Method of activating catalytic alloys



United States Patent US. Cl. 252-477 5 Claims ABSTRACT OF THE DISCLOSURE A method of activating Raney alloys to form new Raney type catalysts by treating Raney alloys with water in the presence of either aluminas, amines, non-N-substituted lactams, N-substituted lactams, oximes, N-substituted acid amides or urea derivatives.

This invention relates to the activation of Raney alloys for obtaining improved Raney type catalysts having excellent activities and durability. More particularly, the invention relates to a method for the activation of Raney alloys, as well as the various modifications thereof, wherein Raney alloys are treated with water in the presence of either aluminas, amines, lactams, oximes, N-substituted acid amides or urea derivatives.

It is well known that Raney catalysts can be prepared by treating an alloy of aluminum with a metal active for catalystic hydrogenation such as nickel, cobalt, iron or copper, i.e. a so-called Raney alloy, with an aqueous solution of a sufficient concentration of a strong inorganic alkali, say, caustic soda to elute the aluminum from the alloy. When a Raney catalyst is prepared in large quantities on a commercial scale by this method, great care must be taken due to the heat and large amount of hydrogen gas which are violently generated from the reaction of aluminum in the alloy with said aqueous solution of a strong inorganic alkali. In addition, there is also the disadvantage that specially designed equipment must be used. Furthermore, the resultant Raney catalyst is deactivated or ignites spontaneously when it comes into contact with air or becomes dry in air, and hence great caution is required in its handling. Consequently, this catalyst is usu ally stored in water or alcohols. However, a decline in its catalytic activity takes place during its storage, and it has a poor durability when used for hydrogenation. Further its regeneration is difficult. Thus, the usual Raney catalyst, prepared by the elution of a major part of the aluminum in the alloy with an aqueous solution of a strong inorganic alkali, had many difficulties in commercial preparation and use because of its high cost, poor durability and delicacy in handling.

In addition, there has also been known a method which comprises treating the Raney alloy with an aqueous solution in which sodium hydroxide is contained in less than its stoichiometric quantity. Also there is known a method wherein the alloy is activated by water, steam or an aqueous solution containing a substance such as cane sugar, salt or sodium carbonate, which plays a role in raising the boiling point of water (US. Pat. 1,915,473). Thus a bulky catalyst containing alumina is obtained. However, for preparing a highly active catalyst by these methods, there is such inconvenience that a very long time is required for sufiicient activation of the alloy.

We have found that certain substances, i.e., aluminas, amines, lactams, oximes, N-substituted acid amides and urea derivatives all have the effect of promoting the activation of the Raney alloys with water and hence improved Raney type catalysts are provided. Specifically, it has been found that when the Raney alloys are treated even at a low temperature in a relatively short time with water in 3,544,485 Patented Dec. 1, 1970 ICC the presence of one or more of the aforesaid substances it is possible to provide new Raney type catalysts which have excellent activity, durability, selectivity, and ease in handling and regeneration. According to the present invention, it is possible to activate the Raney alloys without causing the violent evolution of heat and hydrogen gas as in the prior art, but with controlled evolution. The products thus obtained are improved Raney type catalysts containing alumina which results from the aluminum in the alloy. It is believed that the catalysts have a unique structure judging from the fact that their activities and durabilities are higher than those of any conventional Raney type catalysts.

More specifically, this invention relates to a method of activating Raney alloys which comprises treating a Raney alloy with water in the presence of at least one substance selected from the group consisting of aluminas, amines, non-N-substituted lactams, N-substituted lactams having at least one hydrogen atom on the carbon atom adjacent to the CO group, oximes, N-substituted acid amides having at least one hydrogen atom on either the carbon atom adjacent to the C0 of the amide group or the nitrogen atom of the amide group, and urea derivatives in which each of the two nitrogen atoms of the urea group has one hydrogen atom or in which one of the two nitrogen atoms has one hydrogen atom while the other nitrogen atom has no hydrogen atom.

The Raney alloy to be used in this invention may be any of the alloys consisting of aluminum and metals active for catalytic hydrogenation such as iron, nickel, cobalt or copper. In other words, it may be any of the alloys which are usually known as Raney alloys. Usually, the commercially available alloys are used, i.e. alloys consisting of aluminum and either iron, cobalt, nickel or copper, and preferably those in which the weight ratio of aluminum to these metals is 7:3l:1 and whose particle size is smaller than 50 mesh. Further, mixtures of the Raney alloys may also be used. Also conveniently used are the alloys which contain a third component, for example, such as boron, titanium, chromium, manganese, molybdenum, zirconium, lead, tin and tungsten.

The above-mentioned several substances which are to .be present in treating the Raney alloys with water according to this invention are described below in details. The term promoter, as herein used, denotes the abovementioned substances.

Many types of structurally different aluminas are known. While they are usually represented by the formulas A1 0 A1 O -H O or Al O -3H O, there are many other types of aluminas whose composition cannot be expressed by a simple chemical formula. All of these, however, can be effectively used in this invention as a promoter, Al O -3H O being particularly preferred. For instance, the well-known hydrargillite (gibbsite) and bayerite are expressed by the formula, Al O -3H O. The substance expressed by the formula Al(OH) and generally referred to as aluminum hydroxide can also be used as the promoter because Al(OH) or aluminum hydroxide is a substance consisting presumably of water and alumina or aluminum oxide and it is to be understood that aluminas, as used herein and the appended claims, comprehends this substance also. It is also to be understood that the use of aluminum or such compounds as form aluminas under activating conditions, for example, the inorganic aluminum compounds such as sodium aluminate, alum, aluminum sulfate and aluminum nitrate and the organic aluminum compounds such as aluminum ethoxide and aluminum isopropoxide is also comprehended by this invention.

Any amine can be used as a promoter in this invention. The amines, as herein used, denote the organic bases containing the nitrogen atom. Namely, the compounds having the general formula amines used in this invention are classified as primary,

secondary and tertiary amines and basic compounds containing imino group and, preferably, they are aliphatic amines, aromatic amines, alicyclic amines, heterocyclic amines, amidines and iminourea derivatives. Specific examples of conveniently usable amines are given below, but it is to be understood that the amines usable are not limited to those given.

The primary amines include, for example, methylamine, ethylamine, n-propylamine, n-butylamine, laurylamine, oleylamine, stearylamine, benzylamine, aniline, mand p-phenylenediamine, cyclohexylamine, bornylamine, allylamine, ethanolamine, 4-aminopyridine, 4-aminoquinoline, ethylenediamine, bis-aminomethylcyclobutane, Z-methylpentamethylenediarnine, hexamethylenediamine, trimethyl hexamethylenediamine, decamethylenediamine, dodecamethylenediamine and 0-, mand p-xylylenediamine. The secondary amines include such as dimethylamine, diethylamine, dihexylamine, allylmethylamine, benzylmethylamine, diallylamine, trimethyleneimine, pyrrolidine, piperidine and hexamethyleneimine. The tertiary amines include trimethylamine, triethylamine, dimethylethylamine, benzyldiethylamine, pyridine, N-ethylpiperidine, N-methylpyrrolidine, 2,4,6-trimethylpyridine, 8-hydroxyquinoline and S-methoxyacridine. The amidines include such as formamidine, acetamidine, propionamidine, lauramidine, stearamidine. The iminourea derivatives include such as guanidine, phenylguanidine, creatine, creatinine and arginine.

Compounds which can be converted to amines under activating conditions of the Raney alloys can also be used in this invention instead of the aforementioned amines. Hence, this embodiment is also included in the scope of this invention. The compounds which can be converted to amines, for exampleby hydrogenation, are nitro compounds, nitroso compounds, hydroxylamino compounds, azo compounds, azoxy compounds, hydrazo compounds, nitriles, isonitriles and Schifis bases.

The non-N-substituted lactams to be used in this invention may be any cyclic amides whose amide group does not have a substituent on their nitrogen atom. Specific examples are gamma-butyrolactam, delta-valerolactam, epsilon-caprolactam, zeta-enantholactam, eta-caprylolactam, lambdi-laurolactam and the like.

The N-substituted lactams, having at least one hydrogen atom on the carbon atom adjacent to the CO group, are represented by the general formula wherein R and R are organic radicals and R is either a hydrogen atom or an organic radical. Specific examples of conveniently usable N-substituted lactams are the following: N-methyl-gamma butyrolactam, N-isopropylgamma butyrolactam, N methyl delta valerolactam, N-methyl-epsilon 'caprolactam, N-ethyl-epsilon-caprolactam and N-methyl-3-methyl-deltavalerolactam.

The oximes are classified into aldoxime and ketoxime, but both can be equivalently used in this invention. As specific examples, acetaldoxime, n-butylaldoxime, benzaldoxime, acetophenoneoxime, benzophenoneoxime and cyclohexanoneoxime can be mentione 4 The N-substituted acid amides, having at least one hydrogen atom on either the carbon atom adjacent to the C0 of the amide group or the nitrogen atom of the amide group, are represented by the general formula wherein R is an organic radical and R R R and R respectively represent a hydrogen atom or an organic radical, with the proviso that at least one of them is a hydrogen atom. The conveniently available N-substituted acid amides are, for example, the followings: N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, N,N-dimethylpropionamide, N-hydroxymethyl isobutyramide, N-methyl phenylacetamide and N,N-dimethyl phenylacetamide.

The urea derivatives, in which each of the two nitrogen atoms of the urea group has one hydrogen atom or in which one of the two nitrogen atoms has one hydrogen atom while the other nitrogen atom has no hydrogen atom, are represented by the general formula /N-C ON\ R1 R3 wherein R and R are organic radicals and R is either a hydrogen atom or an organic radical. As specific examples, N,N-dimethylurea, N,N'-diethylurea, N,N,N'-trimethylurea and N,N,N'-triethylurea can be mentioned.

The hereinabove described substances can be used alone or together. Since their use in an excessively small amount does not produce the desired results, they are usually used in an amount of at least by weight of the Raney alloy. The amount of the promoter applied depends on the kind of promoter, the amount of water to be used and the treating temperature. Generally speaking, when promoter is applied greater than one-half, particularly about twice, the weight of the Raney alloy, the activation is promoted effectively. When aluminas are applied as a promoter, much less quantity of them is enough for promotion than those of the other promoters.

In case of applying the promoters, water-soluble ones are preferably chosen except for aluminas. However, those which are insoluble or hardly soluble in water are also applicable. In this case, desirable results are frequently brought about by using suitable solvents which dissolve the promoters and are also miscible with water. Such solvents usually employed are, for example, methanol, ethanol, isopropanol, dioxane, tetrahydrofuran and dimethylformamide.

The water is used in an amount which is essentially sufl'icient for reacting equivalently with the aluminum contained in the alloy, but usually an amount more than twice the equivalent is desirable. When it is desired to erode the alloy slightly or when there is a special reason, the amount of water can suitably be reduced.

One of the features of this invention is that the effective activation of the Raney alloys can be attained under mild conditions of relatively low temperatures and then the degree of erosion of the alloys can be controlled at will. Specifically, the desired end can be attained at a temperature not lower than 0 C. For shortening the time of activation, usually a temperature higher than 10 C. is preferred. Although elevated temperature up to 350 C. can be applied, the preferred temperature is one not exceeding C. from the consideration of the fact that there are slight decreases in the activities of the catalysts prepared at higher temperatures.

The activation can be carried out under atmospheric or higher pressure in the presence of air, nitrogen or hydrogen gases.

It was found that the time required for the activation could be shortened still further by the use of a small amount of an alkaline substance together with the aforesaid specific promoters. The alkaline substances are the following: alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal or alkaline earth metal salts of inorganic or organic weak acids, e.g., carbonates, phosphates, borates, acetates, propionates and phenoxides, alkali metal alcoholates, quaternary ammonium hydroxides, hydrazine hydrate and ammonium hydroxide. As the application of a large quantity of such alkaline substance as alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alcoholates, quaternary ammonium hydroxides or hydrazine hydrate causes the violent evolution of heat and hydrogen gas and then many profitable features of the present invention are lost, the applicable amount of the alkaline substance should be under /5 equivalent to the aluminum contained in the Raney alloy.

As the operating conditions to activate the Raney alloys according to this invention is mild and hence special equipment for the operation are not required, there is the advantage that the operation can be done in the reactor in which the hydrogenation reaction is to be carried out. In this case, it is, of course, possible to adopt a mode wherein the organic compound to be hydrogenated, and, if necessary, hydrogen gas are present together in the reactor. Thus, the activation of the Raney alloy and the hydrogenation of the organic compound can be carried out at the same time. When the organic compound is one Which can be converted to an amine by hydrogenation, the aforesaid reactioins can be carried out merely in the presence of Raney alloy, water, hydrogen gas and the said organic compound. In such a case the amine formed from the said organic compound plays a role of the promoter and still better results are obtained by adding a small amount of the previously noted alkaline substances or catalytically active substances for hydrogenation, e.g. the Raney type catalyst obtained by this invention, Raney nickel, Raney cobalt, nickel boride, palladium on carbon or platinum oxide. In contrast with the conventional process, in which hydrogenation had to be carried out by charging the reactor with the delicate Raney catalyst which had been prepared independently, these embodiments of this invention have great commercial advantages. Hydrogenolysis, reductive alkylation and other reactions can also be carried out in like manner as mentioned above.

The improved Raney type catalysts obtained by this invention are, as previously noted, not only very active and durable but also nonpyrophoric and are not deactivated even when they are dried in air. And after having been used as catalysts for hydrogenations, they can either be used for successive hydrogenations or be stored in slurry or frozen form. Alternatively, they can be dried in air and stored in this state and, as required, be reused for hydrogenations. On the other hand, when their activities are decreased by repeated uses they can be readily regenerated by applying one or more of the following ways: treating with water, treating with water after being admixed with aluminum or a fresh Raney alloy, or treating with an aqueous alkaline solution. Further, the Raney type catalysts obtained by the invention are also excellent in selectivities. For instance, hydrogenation of nitriles with the conventional Raney catalysts results in forming relatively large amounts of secondary amines and other by-products, whereas desired primary amines are formed selectively and in excellent yields with the catalysts of this invention.

The fact that the invention can provide the improved Raney type catalysts having the many characteristics above noted is another important feature of this invention.

The following examples are given to illustrate this invention, but they are not limited to the present invention in any manner, since it is obvious that many variations embraced by the above descriptions of the invention are possible.

Although the general procedures of practising this invention are described below by the instances of hydrogenation reaction, the illustrated methods can be suitably practised in like manner when being applied to the other reactions.

GENERAL PROCEDURES (1) Preparation of catalyst (activation of Raney alloy) Procedure A.--A Raney alloy, water and a promoter or promoters and, if necessary, a suitable solvent and/or a small amount of hydrogenation catalyst and/ or a small amount of an alkaline substance are placed in a vessel. The mixture is stirred for a required time at a prescribed temperature. At this time, if the hydrogen .gas generated is collected in a gas burette in a suitable manner during the course of the reaction, the progress of the activation can be checked. The resultant catalyst is transferred to a hydrogenation reactor immediately or, if necessary, after washing with water or a suitable solvent.

Procedure B.A Raney alloy, Water and a promoter or promoters and, if necessary, a suitable solvent and/or a small amount of a hydrogenation catalyst and/or a small amount of an alkaline substance are placed in a pressure vessel. After replacing the air in the vessel by hydrogen or nitrogen gas, the mixture is stirred for a required time at a prescribed temperature. The resultant catalyst is similarly treated as in Procedure A. After preparation of the catalyst, the 'vessel used for the activation in Procedure A or B can, of course, be utilized as a reactor of successive hydrogenation without transferring the catalyst.

(2) Hydrogenation Procedure C (hydrogenation under ordinary or low pressure).The catalyst prepared by either Procedure A or B and the organic compound to be hydrogenated and, if necessary, a suitable solvent and/or an additive which acts favorably for the hydrogenation (e.g. an alkaline substance in case of the hydrogenation of carbonyl compounds and phenols, and liquid NH in case of nitriles) are placed in an airtight vessel connected with a gas burette to measure the amount of hydrogen gas absorbed. After replacing the air in the vessel thoroughly 'by hydrogen gas, the contents of the vessel are vigorously stirred at a prescribed temperature until the hydrogen uptake ceases.

Procedure D (hydrogenation under high pressure).-The catalyst prepared by either Procedure A or B and the organic compound to be hydrogenated and, if necessary, a suitable solvent and/or an additive such as described in Procedure C are placed in an autoclave. After replacing the air in the autoclave thoroughly by hydrogen gas of the prescribed pressure, hydrogenation is carried out at the prescribed temperature until no further decrease in the hydrogen pressure is observed.

(3) The simultaneous hydrogenation with preparation of the catalyst Procedure E.-A Raney alloy, water, the organic compound to be hydrogenated and a promoter or promoters and, if necessary, a suitable solvent and/ or a small amount of a hydrogenation catalyst and/or an additive are placed in the vessel as described in Procedure C. The subsequent operation is carried out as in Procedure C, but caution must be taken as evolution of hydrogen gas occurs within the reactor.

Procedure F.-A Raney alloy, water, the organic compound to be hydrogenated and a promoter or promoters and, if necessary, a suitable solvent and/ or a small amount of a hydrogenation catalyst and/ or an additive are placed in the vessel equipped with an efficient reflux condenser and the contents are stirred at the prescribed temperature until the evolution of hydrogen gas ceases. iln this case, if the amount of hydrogen generated by the reaction between water and the aluminum contained in the alloy is insufl'icient for completion of the hydrogenation, a hydrogen source such as aluminum grain is required to be present together.

Procedure G.A Raney alloy, water, the organic compound to be hydrogenated and a promoter or promoters and, if necessary, a suitable solvent and/ or a small amount of a hydrogenation catalyst and/ or an additive are placed in an autoclave. The subsequent operation is carried out as described in Procedure D.

In Procedures E, F and G, if the organic compound to be hydrogenated is one which can be converted to an amine by hydrogenation, a promoter is not necessarily needed.

(4) Treatment of the reaction products After completion of the hydrogenation, the catalyst was separated from the reaction mixture and then the reaction products were treated by suitable means according to the cases. In some cases, the reaction products were analyzed by means of gas chromatography. The figures indicated in the Yield column of Table II and III by the notation G.C. are one determined by this means.

EXAMPLE 1 Examples of preparing the catalysts are shown in Table ii. The catalyst of No. 14 was used in the Experiment No. 14 of Example 2 after being washed with water and dried in air.

EXAMPLE 2 Examples in which hydrogenations were effected simultaneously with the preparations of the catalysts are shown in Table III. In Experiments Nos. 16 'and 29' the amounts of residues, after distilling off hexamethyleneimine and hexamethylenediamine from the reaction products, were 2.6% (Experiment No. 16) and 7.1% (Experiment No.

29) of the weights of starting materials respectively.

EXAMPLE 4 After removing the resultant methyl isobutyrate by decantation in Experiment No. 4, Table II, 120 g. of methyl methacrylate was charged in the reactor. The successive hydrogenations were repeated 15 times under identical conditions as in Experiment No. 4 (the reaction temperature spontaneously rose to about 80 C.), and decrease in the catalytic activity was not found. Further, after completion of the last hydrogenation, the catalyst was washed with ethanol, water and then was dried in air. Methyl methacrylate was again hydrogenated with this catalyst under identical conditions as in Experiment No. 4. The result was about the same as that of Experiment No. 4.

EXAMPLE 5 The recovered catalyst of Experiment No. 43, Table II was washed with ethanol, water and then was dried in air at room temperature. After placing this catalyst, 25 g. of resorcinol, 50 ml. of water and g. of sodium hydroxide in an autoclave, hydrogenation was carried out under initial hydrogen pressure of kg./cm. and at 100-110 C. for 6 /2 hours. After filtering off the catalyst, the filtrate was acidified with hydrochloric acid and cooled to 0 C. The precipitated crystal was recrystallized from benzene. The yield of dihydroresorcinol (M.P. 103-4 C.) was 87% of the theoretical.

EXAMPLE 6 The recovered catalyst of Experiment No. 45, Table II. was washed with water and then with ethanol to remove the water. With this catalyst, epsilon-aminocapronitrile was successively hydrogenated under identical conditions as in Experiment No. 45. The results are shown in Table IV.

The recovered catalyst of Experiment No. 62, Table III, Was dried in air at 80 C. This catalyst was charged in an autoclave with 50 g. of adiponitrile and 100 ml. of liquid ammonia. Hydrogenation was carried out under initial hydrogen pressure of 150 kg./cm. at 120-122 C. for 25 minutes. The yield of hexamethylenediamine was 97.1% of the theoretical. Again with this catalyst, adiponitrile was successively hydrogenated 7 times under identical conditions. A decrease in activity of the catalyst was hardly found and the yields of hexamethylenediamine were 96.897.4% of the theoretical throughout the experiments.

EXAMPLE 8 The nickel catalyst prepared under the same conditions of Experiment No. 36, Table I, was washed with water and then wtih methanol. The catalyst was placed in an autoclave with 200 g. of methyl methacrylate, and the hydrogenation was carried out under initial hydrogen pressure of 50 kg./cm. The reaction was over in 5 minutes and the temperature spontaneously rose from 22 C. to 90 C. After separating the resultant methyl isobutyrate from the catalyst, methyl methacrylate was successively hydrogenated 23 times under the same con: ditions described above. The activity of the catalyst was gradually decreased and the time required for completion of the hydrogenation became 65 minutes at the end. The recovered catalyst was washed briefly with methanol and then it was stirred in 60 ml. of water for 2 hours at 85-90 C. Then the catalyst was washed with methanol and again used for the hydrogenation of methyl methacrylate under the same conditions. The regenerated catalyst was so active that the reaction was finished in 6 minutes, and the temperature of the autoclave rose spontaneously from 24 C. to 87 C. The yield of methyl isobutyrate (B.P. '93 C.) was about theoretical.

EXAMPLE 9 4 g. of Raney alloy (Co:Al=1:1), 8 g. of hexamethylenediamine and 35 ml. of water were placed in a vessel equipped with a reflux condenser, following which the mixture was stirred for 70 minutes at 5070 C. The resulting catalyst was washed with water and then water was removed as much as possible from the catalyst. The catalyst was placed in an autoclave with 60 g. of epsilonaminocapronitrile, 5 ml. of water and 0.3 g. of sodium hydroxide. The hydrogenation was carried out under initial hydrogen pressure of kg./cm. at 100-105 C. for 30 minutes. The yield of hexamethylenediamine was 97.6% of the theoretical. When the catalyst was repeatedly used for 18 times without any treatment, its selectivity declined and the yield of hexamethylenediamine decreased to 89.4% of the theoretical. To the mixture of the catalyst and a part of the reaction products 1 g. of alumigenerated catalyst was washed with water and then water was removed as much as possible from the catalyst. With this catalyst, epsilon-aminocapronitrile was hydrogenated under the same conditions mentioned above. The yield of hexamethylenediamine was 97.8% of the theoretical and num grain and 50 ml. of water were added and the adthe fact was owing to the perfect revival of the catalyst mixture was stirred for 30 minutes at 2426 C. The rem selectivlty.

TABLE I [Example 1-Preparation of the catalyst] Raney alloy Cata- Reaction Reaction lyst Pro- Weight Water Solvent temperatime No. cedure Composition (g.) Promoter (g.) (1111.) (m1) Additive (g.) ture, 0. (min.)

Ni:A1=1:1 5 A1203- (2) 100 80-85 200 Cu:Al=1:1 4 A120 (3) 60 100 120 Ni:A1=1:1 6 111203-1120, (3) 50 60-70 180 Ni:Al=4:6 A12O3'3H2O, 5) 100 80 120 NizAl=1z1 2.5 A12Oa'3H2 50 120 90 Ni:A1=1:1 Al2O -3HzO, (1) 100 70-75 310 C0:Al=1:1 10 808,118]? aluminate, 70 Ni:A1=1:1 3 Alniminum ethoxide, 50 90 100 Ni:Al=1:1 5 A1, (0.5) 50 Sodium borate, (0.6) -50 80 NizAl=1z1 20 moi-31120, (1) NaOH, (0.4) 5-7 60 Ni:.Al=1:1 2 n-Butylamine, (7.3)--. 60 90 NizA1=4z6 10 Cyclohexylamine, (10)- 200 100 60 Fe: A1=45255 4 pToluidine, (12) 100 100 150 Co;A l=45:55 10 Hexamethylene dia- 100 80 60 mine, (20).

C0:Al=45 10 Deeamethylene dia- 80 m Ni:Al=1:1 4 50-55 160 17..- A Ni:A1=1:1 2 60-65 120 18 A CuzAl=4z6 2 45-50 100 19 B Ni:A1=1:1 2 -85 20 A Ni:Al=4:6 5 15-20 90 21 B NizAl=1z1 4 Phenylhydroxyla- 70-80 mine, (10).. 22 B NizAl=1z1 4 Azobenzene, (14) 95-100 23 CozAl=1z1 5 Adiponitrile, (15) 50-55 70 24 A NlzAl=1z1 2 Diethylamine, (5) NaOH, (0.1) 27-30 75 25 B Ni:Al=4:6 10 Cyclohexylamine, (10)- 100 Tetramethylammonium 50 60 hydroxide, (0.2). Hemxaethylene, dia- 26 B C0:Al=1:1 5 mine, (20). 100 60 60 Al2O -3HzO,(5). 8-hydroxyquinoline, 27 A Ni:A1=1.1 6 (15). 70 50-57 70 n-Butylamine, (7.5)-.. rum-1.1 a 5 {Ahowmo (1) so NaOH, (0 1) 20 7o Cyclohexylamine, Gu:Al=4:6 3 (10). 50 K200 (0 1) 30 90 1%120 (a.1'H2(()7,)(5) yri ine, Ni.A.l-1.1 2 {MOTBHZO (5) so 90 5 'y-Butyrolactam, (30)-- 80 150 10 B-Valerolaetam, (80) 70 200 :Al 3 e-Caprolactam, (50)--. 100 4 7\-Lan.ro1actam, (10)... 75 NizAl= 1 3 'y-Butyrolactam, (30).- 23-32 70 Ni:Al=4:6 10 6-Valerolactam, (50)... 20-30 100 Ni:Al=1:1 4 e-Oaprolactam, (70)... 21-28 70 CozAl=1z1 10 e-Caprolactam, (70) 24-35 50 C0:A1=45:55 11. 1 -Caprololactam, (50) 20-32 90 Ni:Al=1:1 20 'y-Butyro1aetam,(50) 22-26 110 6Val 1 t 50 (my 41 A Ni:Mo:Al=45:5:50 s gggg gg' 15 10% tetrametl yl ammo- 15-23 70 ]a.prolactam, (10) mum hydroxide aq., (2). 0 90 42 A NEH-L1 4 0 .3 11 t 2 Z8 6) 40 eapro ac am, 43 A C0.A145.55 11.1 K120343320, (3) 30 NaOH, (0.1) 20- 8 80 e-Caprolaetam, (50) 44 A C0:A1=1:1 10 u um 50 Sodium isopropoxide, (2) 3-8 40 isopropoxide, (6). 45 A 4 N-Methyl-v- 90-100 butyrolaetam, (20). 4 A C ;A1=1;1 10 N-Methyl-y- 80-83 220 butyrolaetam, (40). 47 A 1= =1 4 N-Ethyl-e- 75-80 170 caprolaetam, (20). 43 A N1; 1=1;1 2 N-methyl-3-methyl- 94-100 fi-valerolaetam, (10). 49 A C0:A1=45:55 20 N-methyI-a- 0.50 0

I valerolactam, (20).

5 i i i (10) A 1; 1=1;1 va em as am, 50 A12O3-3H2O, (2) 40 55-58 120 N-Methyl-E-valerolac- 51 A N1;Al=1;1 5 tam, (70). 300 Ba(0H)z, (0.14) 30-33 8 A1203-3Hz0, (1)

TABLE I.-Oomtinued Raney alloy Cata- Reaction Reaction lyst Pro- Weight Water Solvent; temperatime No. cedure Composition (g.) Promoter (g.) mm.) (1111.) Additive (g.) ture, 0. (min) 52. A C:A1=45:55 4 Acetoxime, (25) 5O 70-75 180 53. A NizA1=1z1 4 Cyclohexanone EtOH, 40-45 240 oxime, (30). 54 A NizA1=1z1 4 Benzophe- 30 1312011, 38-40 290 B nonegxinle, (1535.) enza oxune, 55 A N1.A11.1 4 {A12OT3H20 (1) 20 EtOH, (40) 24 125 56 A Ni:Al=1:1 4 N, N-di-methyl- 30 -70 215 acetamide, (50). 57 B Ni:Al=4:6 5 N-(x2z(1)e) thy1acetamide, 50 80 120 58 A N1:A1=1:1 4 N,N-Z1imethy1pro so 100 150 pionamide, (40). 59 A Ni:Al=1:1 4 N,N-dimet11y1- 60 NaOH, (0.1) 20-23 propionamide, (40). N, N-d' ethyl- 60 A Ni:Al=1:1 4 propionamide, (40). 60 50-55 125 Al20a- 20, (3) N-hydroxymethyl- 61 A C0:A1=1:1 6 A1isgbugiyramide, (10). 20 i-PrOH Cone NH4OH aq., (4)-..- 60-67 100 2 3' 62 A NizAl=1z1 3 N, N-dimethy1- 20 -85 250 urea, (10). 63 B Ni:A1=1:1 4 N, N, N-tr)imethy1- 40 -96 180 urea, 64 A Ni:A1=4:6 8 N, gY-dimethylurea, L30 Na-OH, (0.07) 48-50 65 A Ni:A1=1:1 10 N,1N- dimethy1urea, 80 Hydrazine hydrate, (0.8).. 18-26 80 N, N, N-triethyl- 66 A Ni:Al=1:1: 6 urea, 50 70-78 120 $203-$130, (0.2)013 rime y mean, 1 57 A N1.A1-1.1 4 4o 55-50 140 TABLE 11 [Example 2-Hydrogenation] Initial Reaction Reac- Catapress tempertime Yield Ex lyst Proce- (kgJ rature tion (moi No No. dure Sample (g1) Solvent (ml.) Additwe (g.) 0111. 0.) (min) Product percent) 1 1 D Diphenyl- EtOH, 30 30-35 65 Diphenyl- 99. 2

v acetylene, ethane. 2 2 D Axzgtopheuone, EtOH, (40) 50 -120 100 Methglphlenyl- 94. 7

car mo 3 3 D Ci(nr11ama1dehyde, i-PrOH, (50) 1% NaOH aq., (0.5).-. 60 60-65 30 Hy1d1t] 1ci{mamyl 93. 6

4 a c0 0 4 4 D Methyl metha- 20-80 10 Methyl 97.8

crylate, (120). isobutyrate. 5 5 C Cyclohexene, (4.1) MeOH, (50) 20 95 Cyc1ohexane 99.5 6.0. 6 6 D N?21)1thalene, EtOH, (100) 100 110-120 80 Tetl'alin 91. 8 2-n1ethy1 penta- 87.2

methylene- 7 7 D Z-methyl gluta- Liquid NHa, (100) 90-95 30 diamine.

ronitrile, (50). 3-methyl 10.4

piperidine 8 C Nitrobenzene, (5)- EtOI-I, (30) 25-27 25 niline 100 6.0. 9 D Phen 0) EtOH, (100) NaOH, (0.5)- 80 90-100 60 Cyclohexanol.-. 95. 1 10 D Naphthalene, (52). EtOH, (100) 100 110-118 65 Tetralin 93.6 11 C Cyclohexene, MeOH, (50) 20 90 Cyc1ohexane 99.6 (3.0.

12 1) Met11y1 metha- 100 25-70 25 Methyl 98.8

crylate, (120). butyrate. 13 D 2-butyn(i%1),4- EtOH, (80) 75 105-110 450 2-lutene-L4- 91.7

1 14 D Adiponitrile, Liquid NHa, (100) 100 120 80 Hexamethylene 95.4

00 diamine. 15 D Sebaoonitrile, Liquid NH (100) 110 115-120 Dgoamethylene 94.8 lamme. 16 C p-giggotoluene, MeOH, (50) H20, (1) 21-26 34 p-To1uidine. 98.7 17 c Cyciohxene, MeOH, 50 1s 65 Cyc1ohexane-- 99. a (3.0.

18 D Bexllgizofihenone, EtOH, (60) 1% NaOH aq., (0.5)--- 70 120-125 25 Benzhydr01 96. 8 19 O Ethyloinnmnate, EtOH, (40) 1. 25 12 Ethyl hydro- 100 6.0. 1 cinnamate. 20 1) EtOH, (100 1 NaOH aq. 0.5)-.. 60 50-55 20 Benzhydrolun. 98.5

Benzophenoue,

TABLE II [Example 2Hydrogenation] Initial Reaction Reac- Cataress tempertime Yield Ex. lyst ProcekgJ rature tion (mol N 0. N 0. due Sample (g.) Solvent (1111.) Additive (g.) cmfi) 0.) (min.) Product percent) Cyclohexyl- 53. 7

amine. 21. 21 D Aniline, (50) Cyclohexane, (50) 90 190-205 370 Dicyglohexyl- 21.6

ammo Aniline 19. 2 22 22 D m-Nitroacetophe- EtOH, (100) 65 80-90 120 m-Aminoaceto- 97. 2

none, (17). phenone. 23"-.- 23 D e-AJIliXlOCB-DIOIJI- Liquid NH (50) 75 110-120 50 Hexamethylene- 95. 2

trile, (50). diamine. 24 24 O Oflelghexen MeOH, (50) 40 Cyclohexane- 100 (3.0. 25--- 25 D Methyl metha- 100 80-70 15 Methyl 98.1

crylate, (120). isobutyrate. 26 26 D Adiponitrile, (50).. Liquid NH ,(70) 120 120 50 Hefiamethylene 97.6

amine. 27 D Quinoline, (20)---- 1515011, (60) 140 60-64 130 1,2,3,4-tetrahy- 96. 7

droquinoline. 28 28 C Cyclohexene, (4.1)- MeOH, (50) 20 35 Cyc1ohexane 100 G.C. 29 29 D Benggghenone, EtOH, (60) 50 110 20 Benzhydrol 30.-- 30 D Methyl methacryl- 1 0 30-80 2 Methyl-isobuty- 97. 7

ate, (30). rate. 31 31 D Benzene, (30).-. 80 100-140 180 Cyc1ohexane. 91 32.-- 32 D Benzil, EtOH, (150) 10% NaOH aq., (0.5)-- 100 60-65 60 Hydrobenzoin-.- 92.3 33 33 D Styrene, (200)- 100 50 30 Ethylbenzene.-. 97. 4 34-...-- 33 C Cyclohexanon EtOH, 1% NaOH aq., (1) 21 200 Cyclohexyla- 87 oxime, (2). mine. 35 34 D Furiural, (32)-- EtOH, (70) 70 130-150 220 Tetrahydro- 83.6

iurfuryl alcohol. 36 35 D t,t,c-Cyclodode- MeOH, (150) 100 40-45 75 Cyclododecanm- 98 G.C

catriene, (50). 37 36 D cycgnexanone, EtOH, (50) 1% NaOH aq., (1) 50 60-70 Cyclohexanol--- 96. 7 38"-.. 37 C Diphelggacetyli-PrOH, (100) 20-25 60 Diphenylethane. 98. 8

ene, 39 37 D Benzhydrol, (18).- EtOH, 130-150 85 Diphenylmeth- 86 ans.

Hexamethylene- 98.77 (3.0 40 38 D Adiponitrile. (100)-, Liquie N11 (100) 80 120 50 diamine.

Hexamethylene- 1.23 6.0.

lmene. 41 39 D Sebaconitrile, (80). Liquid NH (120) 120-122 50 Decamethyl- 98.2

ene dlannne. 42"..- 40 D Valeronitrile, Liquid NH (50) 120 125-127 30 Pentylamine.--. 97.8 43 41 D p-NittosodimethtOH, (80) 120 25 25 p-Aminodi- 95. 3

y aniline, (15). methylaniline. 44---" 42 C m-Dinittobenz- EtOH, (50). 20-31 35 m-Phenylene- 97. 4

ene, (4.6). diamlne.

/ fiexagiethyl- 99.26 G.C. ene amine. 4 43 D ei fin z gg Llquid N 3, 80 118-122 20 EmmethYlene, 0.74

' nnine.

Hexag ethyL 98.14 G.C.

1 mine. 46".-- 44 D Adlponitrile, 100)- Liquid N113, (10o 120 118-122 45 g eneimine. 1.86 G.O. 47 45 D Cilnmaldehyde, EtOH, (70) 1% NaOH aq., (1) 45 50-60 35 fiyiinilciimamyl 94.3

e. co 0 48. 46 D -Amin0caproni- Liquid NH (150) 120-125 25 Hexamethylene- 97.2

trile, (100 diamine. 49 45 G Cyclohexanone- EtOH, (25) 26 230 Cyclohexyla- 87 oxime, (4). mine. 50 47 D 3-nitro-4-methyl EtOH, (100) 80 -100 35 3-amino-4-meth- 93.2

acetophenone, ylacetophe- 34 none. 51 48 D Oleic acid, (45)..-- EtOH, (200)- 70 80-87 75 Stean'c acid 97. 6 52 49 D Adiponitrile, Liquid NHa, 00) 130 -115 60 Hexamethyl- 96. 8

ene dlamine. 50 C Styrne, (13) MeOH, 26-32 40 Ethylbenzene--. 99.8 G.C. 51 D N?i5l)ithalene, EtOH, (40).. 70 -130 110 Tetralin- 92 52 D Cyclohexanonei-PrOH, (80)- 50 70-80 80 Cyclohexyl- 93. 6

oxime, (55). amine. 53 D Acetophenon EtOH, (100)- 1% NaOH aq., (2)"..- 70 60-65 30 Methglphlenyl- 97. 2 car mo 54 C Cyclohexene, (4.1) MeOH, (50)- 25 45 Cyclohexane 99.8 G.C 55 D Bengaldehyde, MeOH, (100) 1% N aOH aq., (1) 50 54-57 50 Benzyl alcohol" 91. 3 56 D Hydroquinone, EtOH, (100) 5% NaOH aq., (1) 60 100-130 120 (Iggglehexaen-IA 98. 9

1o 57 D Methyl meta- 80 21-53 6 Methyl 150- 98. 1

acrylate, (30). butyrate. 58 D Mesityloxide, (45) MeOH, (50) 1% NaOH aq., (1) 75 60-65 140 Methyl i50- 95.2

butylcarbinol. 59 D Mesityloxide, (45) MeOH, (50) 1% NaOH aq., (1)--. 75 60-65 80 ethyl 150- 96. 1

butyleaxbinol. 60 D Mesityloxide, (45) MeOH, (50) 1% NaOH aq., (1)--- 75 60-65 110 Methyl 150- 94. 7

butylcarbinol. 61 D 1,2-dicyano Liquid NH (50) 90 105-110 25 1,2-diamino- 84. 5 cyclobutane, methyl cycloutane. 65 62 D Prg argyl alcohol, 40-50 30 Propanol 95. 4 66 63 C p-Nittotoluene, MeOH, (30) 1120, (0.5) 27-30 45 p-T01uidnie- 97. 3

67- 64 D Styrene, (100)- 85 30-66 25 Ethy1benzene 96. 5 68 65 D Phenol, (130)-. EtOH, (150) 'NaOH, (1) 105-110 75 Cyclohexanol--- 97.4 69-- 66 D Propiophenone, EtOH, (100) 1% NaOH aq., (2).--. 65 70-80 110 Ethylphenyl. 89. 6

70- 67 D Benzophenone- EtOH, (80) 54 78-81 55 Benzhydryl- 94. 2

oxime, (19.7). v 1 amine.

TABLE III.Contin ued Initial Reaction Reac- Raney alloy tion time (min.) Products Yield (mole percent) press temper- (kg./ ature em C.)

Solvent (mL) Additive (g.)

Water (ml.) Sample (g.)

Proce- W elg;: Ex.No. dure Composition (g.) Promoter (g.)

84-91 175 Vanillylalcohol.

Al203-3Hz0, 4 Nzglog-dimethylurea, 50 Vanillin, (18) EtOH, (40) 8 Trime thyleneurea,

NizAl=lz1 NizAl 85-94 185 Propionamide--- 345 Dihydroresorcin01 100 Resorcinol, (55) Sodiumisoprourea, (12). poxide, (0.4).

1 Hours.

We claim:

1. A method of activating Raney allows which comprises reacting at a temperature within the range of 0-350 C. a Raney alloy with water containing at least one substance, in an amount of at least 5% 'by weight based on the weight of said Raney alloy, selected from the group consisting of aluminas, non-N-substituted lactams of the formula wherein R is an alkylene group, N-substituted lactams of the formula wherein R is an alkylene group and R and R are alkyl, oximes of the formula wherein each R is individually selected from the group consisting of hydrogen and a hydrocarbyl group, N-substituted acid amides of the formula wherein R R R R and R are each selected from the group consisting of hydrogen and hydrocarbyl, at least one of R R R R and R being hydrogen, and urea derivatives of the formula wherein R is hydrogen or an alkyl group and R and R are alkyl, said Water containing 0- /5 equivalent amount of an alkali metal hydroxide based on the aluminum content of the alloy.

2. The method according to claim 1 wherein said reac tion is effected at a temperature ranging from 10 to C.

3. The method according to claim 1 wherein said reaction is effected in the co-presence of a solvent of said substance.

4. The method according to claim 1 wherein said reaction is eifected in the co-presence of the copound'to be hydrogenated and hydrogen.

5. The method according to claim 4 wherein said reaction is effected in the co-presence of a solvent of said compound to be hydrogenated.

References Cited UNITED STATES PATENTS 1,628,190 5/1927 Raney 252477R 2,326,275 8/ 1943 Zeltner 252472X 2,328,140 8/1943 Hahn 252477X 2,650,204 8/1953 Reynolds et a1. 252476 2,402,626 6/1946 Howk 252477X 3,235,513 2/1966 Jung et al 252--477X PATRICK P. GARVIN, Primary Examiner US. Cl. X.R. 252472, 476 

